KR20160056170A - Thermoplastic resin composition, and molded articles made therefrom - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, and a molded product comprising the same. The thermoplastic resin composition comprises: a first thermoplastic polymer; and a second thermoplastic polymer, wherein the first thermoplastic polymer is a block copolymer including a plurality of polymer blocks, and comprises one or more random copolymers of the polymer blocks. One or more structure units of the first thermoplastic polymer and a structure unit of the second thermoplastic polymer are stereoisomer.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic resin composition,

A thermoplastic resin composition and a thermoplastic resin composition.

From the viewpoint of environmental protection, interest in biodegradable resins such as aliphatic polyesters is increasing. Among biodegradable resins, polylactic acid (or polylactide) has a melting point as high as 160 to 170 占 폚 and excellent transparency. Lactic acid, which is a raw material of polylactic acid, can be obtained from renewable resources such as plants. Since the decomposed product of polylactic acid is lactic acid, carbon dioxide and water harmless to human body, polylactic acid can be used for various purposes such as medical supplies.

Polylactic acid has higher strength than conventional resins such as HIPS (High Impact PolyStyrene) and ABS (Acrylonitrile-Butadiene-Styrene), but has poor impact resistance and heat resistance. Therefore, it is necessary to improve the impact resistance and heat resistance of the polylactic acid.

When a conventional impact modifier capable of improving the impact resistance of polylactic acid is added, the impact resistance of the polylactic acid is improved but the heat resistance may be lowered. On the other hand, when a conventional heat resistance improving agent capable of improving the heat resistance of polylactic acid is added, the heat resistance of the polylactic acid is improved but the impact resistance may be lowered.

Therefore, there is a demand for a method for improving impact resistance without lowering the heat resistance of polylactic acid.

One aspect is to provide a novel thermoplastic resin composition.

Another aspect is to provide a molded article made of the thermoplastic resin composition.

According to one aspect,

A first thermoplastic polymer; And

And a second thermoplastic polymer,

Wherein the first thermoplastic polymer is a block copolymer comprising a plurality of polymer blocks, at least one of the plurality of polymer blocks including a random copolymer,

There is provided a thermoplastic resin composition wherein at least one structural unit of the first thermoplastic polymer and a structural unit of the second thermoplastic polymer are stereoisomers.

According to another aspect, there is provided a molded article made of the above-mentioned thermoplastic resin composition.

According to one aspect, the impact resistance and heat resistance of a resin composition containing polylactic acid can be improved by including a block copolymer including a random copolymer block [an inorganic material].

1 is a transmission electron microscope (TEM) image of the thermoplastic resin composition prepared in Example 5. Fig.
2 shows the results of differential scanning calorimetry (DSC) analysis of the thermoplastic resin composition prepared in Example 5. Fig.
Fig. 3 shows the results of evaluation of impact resistance of the thermoplastic resin compositions prepared in Examples 5 to 7 and Comparative Example 6. Fig.
4 shows the results of evaluating the impact resistance of the thermoplastic resin compositions prepared in Examples 8 to 10 and Comparative Example 6. Fig.

Hereinafter, the thermoplastic resin composition according to the exemplary embodiments and the molded article made of the thermoplastic resin composition will be described in more detail.

The term " comprising "or" containing "in this specification is intended to encompass the subject component or constituent without limitation of the specific mode and means that additional constituent or component Is not excluded.

As used herein, "lactide" includes L-lactide consisting of L-lactic acid, D-lactide composed of D-lactic acid, and meso-lactide composed of L-lactic acid and D-lactic acid.

As used herein, "polylactic acid" means all polymers including repeating units formed by ring-opening polymerization of lactide monomers. The polymer includes a homopolymer or a copolymer, and is not limited to the specific embodiment in which the polymer is present. For example, the polymer may be used in various forms such as a crude or purified polymer after ring-opening polymerization is completed, a polymer contained in a liquid or solid resin composition before molding the product, or a polymer contained in a plastic, film, .

In the present specification, "poly-L-lactic acid" means a polymer composed of structural units derived from L-lactic acid formed by ring-opening polymerization of L-lactide monomer.

In the present specification, "poly-D-lactic acid" means a polymer composed of D-lactic acid-derived structural units formed by ring-opening polymerization of D-lactide monomer.

"Steroisomer" in this specification means an enantiomeric relationship having the same chemical formulas and structural formulas but with different configurations in three dimensions. For example, when one polymer is stereoisomeric with another polymer, the structural units contained in one polymer and the structural units contained in the other polymer have the same chemical formula and include a chiral center but have a mirror image symmetry relationship with each other. For example, one polymer may be referred to as a chiral polymer and the other polymer as an antichiral polymer, among the two polymers that are stereoisomeric.

As used herein, "random copolymer" means a polymer in which structural units derived from two or more monomers are randomly linked by covalent bonds.

As used herein, the term "block copolymer" refers to a copolymer comprising two or more polymer blocks which contain different structural units and are linked by covalent bonds.

As used herein, the term "thermoplastic resin" is a resin whose flexibility increases with increasing temperature.

As used herein, "monomer" is a monomolecular compound that can be used in the preparation of a polymer to form structural units of the polymer.

The thermoplastic resin composition according to one embodiment comprises a first thermoplastic polymer; And a second thermoplastic polymer, wherein the first thermoplastic polymer is a block copolymer comprising a plurality of polymer blocks, wherein at least one of the plurality of polymer blocks comprises a random copolymer, and one of the first thermoplastic polymer The above structural units and the structural units of the second thermoplastic polymer are stereoisomers.

The first thermoplastic polymer includes a polymer block composed of a random copolymer. The polymer block composed of the random copolymer may have flexibility by lowering the glass transition temperature or melting point by irregularly including a plurality of different structural units. For example, in the case of a crystalline polymer, flexibility can be increased by inhibiting crystallization occurring in a homopolymer block composed of one structural unit. By including a polymer block of a random copolymer with increased flexibility, the flexibility of the first thermoplastic polymer can be increased. As a result, the impact resistance of the thermoplastic resin composition comprising the first thermoplastic polymer containing the random copolymer block having increased flexibility can be improved.

Also, since at least one structural unit and a structural unit included in the second thermoplastic polymer among the plurality of structural units included in the first thermoplastic polymer are stereoisomers, these structural units can form a sereo-complex . That is, the first thermoplastic polymer and the second thermoplastic polymer physically form a stereo complex to improve the thermal stability of the resin composition. For example, by melting the first thermoplastic polymer and the second thermoplastic polymer complementarily, the melting point of the resin composition can be increased.

The random copolymer may be at least one selected from the group consisting of an ether monomer, an olefin monomer, a vinyl monomer, a polyol monomer, a polyacid monomer, an isocyanate monomer, an acrylate monomer, a vinyl alcohol monomer, an ethylenic monomer, And a structural unit derived from at least two monomers selected from the lactone-based monomers.

Specifically, the random copolymer may be selected from the group consisting of lactic acid, styrene, vinylnaphthalene, methyl methacrylate, caprolactone, valerolactone, butyrolactone, butadiene, isobutylene, styrene-butadiene, methylsiloxane, ethylene, , 4-methyl-pentene, norbornyl ethyl styrene, hexamethyl carbonate, hexyl norbornene, butyl succinate, dicyclopentadiene, cyclohexyl ethylene, 1,5-dioxepan- , Isoprene, 3-hydroxybutyrate, 2-hydroxymethacrylate, N-vinyl-2-pyrrolidone, 4-acryloylmorpholine, ethylene oxide, ethylene glycol, acrylonitrile, vegetable oil derivatives, propylene At least two monomers selected from glycol, tetramethylene ether glycol, para-dioxanone, propylene carbonate, tetramethylene adipate, terephthalate, butylene adipate, and butylene succinate ≪ / RTI >

The random copolymer may include a structural unit derived from a monomer that imparts elasticity to the polymer and a structural unit derived from a monomer having a different structure. For example, the monomer that imparts elasticity to the polymer is selected from among an ether-based monomer, an olefin-based monomer, a vinyl-based monomer, a polyol-based monomer, an isocyanate-based monomer, an acrylate-based monomer, an ester-based monomer, One or more monomers.

Specifically, the monomer that imparts elasticity to the polymer is selected from the group consisting of caprolactone, valerolactone, butyrolactone, butadiene, isobutylene, styrene-butadiene, methylsiloxane, ethylene, Methylene carbonate, hexyl norbornene, butyl succinate, dicyclopentadiene, 1,5-dioxepan-2-one, isoprene, 3-hydroxybutyrate, ethylene oxide, ethylene glycol, acrylonitrile, vegetable oil derivatives, At least one monomer selected from the group consisting of propylene glycol, tetramethylene ether glycol, para-dioxanone, propylene carbonate, butylene adipate, and butylene succinate.

The monomer having a different structure from the monomer that imparts elasticity to the polymer is not particularly limited as long as it is a monomer capable of forming a random copolymer with a monomer that imparts elasticity to the polymer.

For example, the random copolymer may comprise a first structural unit derived from D-lactic acid and a second structural unit derived from a monomer having a structure different from D-lactic acid. Specifically, the random copolymer may include a first structural unit derived from D-lactic acid and a second structural unit derived from caprolactone.

On the other hand, the random copolymer may have a composition comprising 10 to 50% by weight of the first structural unit and 50 to 90% by weight of the second structural unit. For example, the random copolymer may comprise 10 to 40% by weight of the first structural unit and 60 to 90% by weight of the second structural unit. For example, the random copolymer may comprise 10 to 30% by weight of the first structural unit and 70 to 90% by weight of the second structural unit. For example, the random copolymer may comprise from 10 to 25% by weight of the first structural unit and from 75 to 90% by weight of the second structural unit. A thermoplastic resin composition having improved impact resistance and heat resistance can be obtained by blending a block copolymer comprising a random copolymer block having a content range of the first structural unit and the second structural unit. If the content of the first structural unit is too low, the crystallinity of the polymer block including the random copolymer increases, and the impact resistance may be lowered. For example, the substantially random copolymer may have physical properties such as polycaprolactone, so that compatibility with poly L-lactic acid may be deteriorated. If the content of the first structural unit is too high, for example, the random copolymer may have physical properties such as poly-D-lactic acid and the impact resistance may be deteriorated. For example, the random copolymer may contain 10 to 50% by weight of a structural unit derived from D-lactic acid and 50 to 90% by weight of a structural unit derived from caprolactone.

Alternatively, the weight ratio of the first structural unit to the second structural unit in the random copolymer may be 10:90 to 50:50. For example, the weight ratio of the first structural unit to the second structural unit in the random copolymer may be 10:90 to 25:75. For example, the weight ratio of the structural unit derived from D-lactic acid to the structural unit derived from caprolactone in the random copolymer may be 10:90 to 50:50.

The glass transition temperature (Tg) of the random copolymer may be less than 0 ° C. For example, the glass transition temperature (Tg) of the random copolymer may be less than 0 ° C to -50 ° C. For example, the glass transition temperature (Tg) of the random copolymer may be from -20 占 폚 to -50 占 폚. For example, the glass transition temperature (Tg) of the random copolymer may be from -25 ° C to -50 ° C. For example, the glass transition temperature (Tg) of the random copolymer may be from -30 캜 to -50 캜. As the glass transition temperature of the random copolymer is lower than 0 占 폚, the impact resistance of the thermoplastic resin composition containing the block copolymer containing the polymer block made of the random copolymer can be improved. If the glass transition temperature of the random copolymer is too low, the flexibility of the random copolymer may increase and the toughness may be lowered. If the glass transition temperature is too high, the impact resistance may be lowered.

The weight average molecular weight of the random copolymer may be from 30,000 to 100,000. For example, the weight average molecular weight of the random copolymer may be from 30,000 to 85,000. For example, the weight average molecular weight of the random copolymer may be from 30,000 to 70,000. A thermoplastic resin composition having improved impact resistance in the weight average molecular weight range of the random copolymer can be obtained. If the weight average molecular weight of the random copolymer is too low, the flexibility may be low and the impact strength may be deteriorated. If the weight average molecular weight of the random copolymer is too high, the flexibility may be excessively increased and the heat resistance of the entire resin composition may be deteriorated.

The block copolymer may comprise a first polymer block comprising a random copolymer and a second polymer block comprising a homopolymer. By including the polymer block including the random copolymer, the impact resistance of the thermoplastic resin composition containing the block copolymer can be improved. In addition, the block copolymer includes a polymer block including a homopolymer, and the thermoplastic resin composition may have improved heat resistance by forming a stereomeric complex with the second thermoplastic polymer. For example, the homopolymer may be poly-D-lactic acid.

The block copolymer may comprise 50 to 90% by weight of a first polymer block comprising a random copolymer and 10 to 50% by weight of a second polymer block comprising a homopolymer. For example, the block copolymer may comprise 50 to 80% by weight of the first polymer block and 20 to 50% by weight of the second polymer block. For example, the block copolymer may comprise 50 to 70% by weight of the first polymer block and 30 to 50% by weight of the second polymer block. A thermoplastic resin composition having an impact resistance and heat resistance improved in the content range of the first polymer block and the second polymer block can be obtained. If the content of the first polymer block is too low, the flexibility of the block copolymer may decrease, and the impact resistance of the thermoplastic resin composition may be lowered. If the content of the first polymer block is too high, the flexibility of the block copolymer increases, and the toughness of the resin composition containing the block copolymer may be lowered.

Alternatively, the weight ratio of the first polymer block to the second polymer block in the block copolymer can be 50:50 to 90:10. For example, in a block copolymer, the weight ratio of the first polymer block to the second polymer block may be 50:50 to 70:30.

The weight average molecular weight of the block copolymer including the random copolymer block may be 50,000 to 150,000. For example, the weight average molecular weight of the block copolymer may be from 50,000 to 100,000. For example, the weight average molecular weight of the block copolymer may be from 50,000 to 80,000. A thermoplastic resin composition having improved impact resistance and heat resistance in the weight average molecular weight range of the block copolymer can be obtained. If the weight average molecular weight of the block copolymer is too low, the resin composition may exhibit the same properties as the random copolymer and may have a low heat resistance. If the weight average molecular weight of the block copolymer is too high, characteristics such as PDLA (poly-D-lactic acid) And the impact strength of the resin composition may be lowered.

For example, a block copolymer comprising a polymer block comprising a random copolymer of caprolactone and D-lactic acid and a polymer block comprising poly-D-lactic acid may be represented by the following formula (1).

≪ Formula 1 >

M is the weight fraction of the D-lactic acid structural unit, x is the weight fraction of the random copolymer block and y is the weight fraction of the homopolymer block, n + m = 1, x + y = 1, 0.5? n? 0.9, 0.1? m? 0.5, 0.5? x? 0.9, 0.1? y? 0.5 and a weight average molecular weight of 50,000 to 150,000.

The block copolymer may have a first melting point of 30 to 60 占 폚 and a second melting point of 110 to 170 占 폚. The first melting point corresponds to the melting point of the polymer block including the random copolymer and the second melting point corresponds to the melting point of the polymer block including the homopolymer. For example, the block copolymer may include a first melting point of 30 to 60 占 폚 and a second melting point of 110 to 170 占 폚. For example, the block copolymer may comprise a first melting point of 30 to 55 占 폚 and a second melting point of 110 to 160 占 폚. For example, the block copolymer may include a first melting point of 30 to 50 占 폚 and a second melting point of 110 to 155 占 폚. The impact resistance and heat resistance of the thermoplastic resin composition comprising the block copolymer can be improved by simultaneously including the first melting point of 60 ° C or less and the second melting point of 110 ° C or more. If the first melting point due to the polymer block containing the random copolymer is too high, the flexibility of the block copolymer may be lowered and the impact resistance of the thermoplastic resin composition may be lowered. If the second melting point due to the polymer block containing the homopolymer is too low, the mechanical strength of the thermoplastic resin composition may be lowered.

In the thermoplastic resin composition, the second thermoplastic polymer may be poly-L-lactic acid. Poly-L-lactic acid is a polymer comprising a lactic acid structural unit of formula (2), which is a chiral polymer comprising a chiral center in the lactic acid structural unit and is represented by the R / S configuration, It is lactic acid. The poly-L-lactic acid may form a stereocomplex with a poly-D-lactic acid block which is an enantiomer contained in the block copolymer.

(2)

When the at least one structural unit of the first thermoplastic polymer comprises D-lactic acid, the second thermoplastic polymer may be a poly-L-lactic acid comprising L-lactic acid which is a stereoisomer of D-lactic acid. Also, if the at least one structural unit of the first thermoplastic polymer comprises L-lactic acid, then the second thermoplastic polymer may be a poly-L-lactic acid comprising D-lactic acid which is a stereoisomer of L-lactic acid.

The poly-L-lactic acid may have a weight average molecular weight of 10,000 to 500,000. For example, the poly-L-lactic acid may have a weight average molecular weight of 100,000 to 300,000. If the weight average molecular weight of the poly-L-lactic acid is less than 10,000, the mechanical properties of the thermoplastic resin composition may be deteriorated. If the weight average molecular weight exceeds 500,000, the processing may be difficult.

The optical purity of the poly-L-lactic acid may be 90% or more. For example, the optical purity of the poly-L-lactic acid may be 93% or more. For example, the optical purity of the poly-L-lactic acid may be 95% or more. For example, the optical purity of the poly-L-lactic acid may be 97% or more. If the optical purity of the poly-L-lactic acid is 90% or less, the mechanical properties may deteriorate.

And 5 to 30% by weight of the first thermoplastic polymer relative to the total weight of the thermoplastic resin composition. For example, 10 to 30% by weight of the first thermoplastic polymer relative to the total weight of the thermoplastic resin composition. For example, 10 to 25% by weight of the first thermoplastic polymer relative to the total weight of the thermoplastic resin composition. A thermoplastic resin composition having improved impact resistance and heat resistance in the first thermoplastic polymer content range can be obtained. If the content of the first thermoplastic polymer is too low, it corresponds to the case where the thermoplastic resin composition contains substantially only the second thermoplastic polymer, so that the impact resistance of the thermoplastic resin composition may be deteriorated. If the content of the first thermoplastic polymer is too high, the toughness of the thermoplastic resin composition may be lowered at room temperature, and the heat resistance may also be lowered.

And 65 to 90% by weight of the second thermoplastic polymer relative to the total weight of the thermoplastic resin composition. For example, the thermoplastic resin composition may include 70 to 90% by weight of the second thermoplastic polymer relative to the total weight of the thermoplastic resin composition. For example, the thermoplastic resin composition may contain 75 to 90% by weight of the second thermoplastic polymer relative to the total weight of the thermoplastic resin composition. A thermoplastic resin composition having improved impact resistance and heat resistance in the second thermoplastic polymer content range can be obtained. If the content of the second thermoplastic polymer is too low, the toughness of the thermoplastic resin composition may be lowered at room temperature and the heat resistance may be lowered. If the content of the second thermoplastic polymer is too high, it corresponds to the case where the thermoplastic resin composition contains substantially only the second thermoplastic polymer, so that the impact resistance of the thermoplastic resin composition may be deteriorated.

In the thermoplastic resin composition, the weight ratio of the first thermoplastic polymer to the second thermoplastic polymer may be from 5:95 to 35:65. For example, the weight ratio of the first thermoplastic polymer to the second thermoplastic polymer in the thermoplastic resin composition may be 10:90 to 30:70. For example, the weight ratio of the first thermoplastic polymer to the second thermoplastic polymer in the thermoplastic resin composition may be 10:90 to 20:80.

The thermoplastic resin composition may further include a plasticizer. By further including the plasticizer, the impact resistance and heat resistance of the thermoplastic resin composition can be further improved.

The plasticizer may be a synthetic plasticizer, a vegetable plasticizer, or a mixture thereof. The content of the plasticizer may be 1 to 5% by weight based on the total weight of the thermoplastic resin composition. For example, the content of the plasticizer may be 1 to 4% by weight based on the total weight of the thermoplastic resin composition. For example, the content of the plasticizer may be 2 to 4% by weight based on the total weight of the thermoplastic resin composition. The impact resistance and heat resistance of the thermoplastic resin composition can be improved in the content of the plasticizer. If the content of the plasticizer is too low, the plasticizer can not act as a plasticizer. If the content of the plasticizer is too high, the heat resistance of the thermoplastic resin composition may be deteriorated.

Examples of synthetic plasticizers include phthalate plasticizers, adipate plasticizers, silicone plasticizers, trimethylolpropane-tri (2-ethylhexanoate) and benzoic acid, 2,2-bis (2-ethylhexanoyloxymethyl) A mixture of 2-ethylhexanoic acid, 2,2-bis (beoyloxy-methyl) butyl ester and trimethylolpropane-tribenzoate, mixed alcohol esters, citric acid esters or combinations thereof.

Specific examples of synthetic plasticizers include, but are not limited to, dioctyl terephthalate, dioctyl (nonyl) terephthalate, trimethylol propane-tri (2-ethylhexanoate) and benzoic acid, 2,2- bis (2-ethylhexanoyloxymethyl ) Butyl ester, a mixture of 2-ethylhexanoic acid, 2,2-bis (beoyloxy-methyl) butyl ester and trimethylolpropane-tribenzoate, mixed alcohol esters, citric acid esters or combinations thereof .

Vegetable plasticizers may be vegetable oils, modified vegetable oils, and the like. Modified vegetable oils are reaction products of vegetable oils with other monomers. The modification may be, for example, epoxydization, maleinization or acrylation. The vegetable oil may be soybean oil, linseed oil, palm oil or a combination thereof. The modified vegetable oil may be an epoxidized soybean oil, an acrylated soybean oil, a maleated soybean oil, an acrylated-epoxidized soybean oil, or a combination thereof.

For example, the plasticizer may be a reactive plasticizer. The reactive plasticizer may be disposed on the surface of the first thermoplastic polymer to form a surface morphology of the first thermoplastic polymer in the thermoplastic resin composition. In addition, the reactive plasticizer may increase the binding force of the first thermoplastic polymer and the second thermoplastic polymer by forming a bond with the first thermoplastic polymer and / or the second thermoplastic polymer, such as reactive groups such as epoxy groups.

In the thermoplastic resin composition, 5 to 30% by weight of the first thermoplastic polymer, 65 to 90% by weight of the second thermoplastic polymer, and 1 to 5% by weight of the plasticizer based on the total weight of the resin composition. For example, the thermoplastic resin composition may contain 5 to 25% by weight of the first thermoplastic polymer, 70 to 90% by weight of the second thermoplastic polymer, and 1 to 5% by weight of the plasticizer based on the total weight of the resin composition. For example, the thermoplastic resin composition may contain 5 to 20% by weight of the first thermoplastic polymer, 75 to 90% by weight of the second thermoplastic polymer, and 1 to 5% by weight of the plasticizer based on the total weight of the resin composition. For example, the thermoplastic resin composition may contain 5 to 15% by weight of the first thermoplastic polymer, 80 to 90% by weight of the second thermoplastic polymer, and 1 to 5% by weight of the plasticizer based on the total weight of the resin composition. An impact resistance and heat resistance improved in the composition range of the thermoplastic resin composition can be obtained.

Further, the thermoplastic resin composition may further contain a nucleating agent. By further including a nucleating agent, the crystallization rate of the polylactic acid can be improved to further improve the heat resistance.

The content of the nucleating agent may be 0.1 to 10% by weight based on the total weight of the thermoplastic resin composition. For example, the content of the nucleating agent may be 0.1 to 6% by weight based on the total weight of the thermoplastic resin composition. For example, the content of the nucleating agent may be 0.1 to 4% by weight based on the total weight of the thermoplastic resin composition. For example, the content of the nucleating agent may be 0.5 to 3% by weight based on the total weight of the thermoplastic resin composition. The impact resistance and heat resistance of the thermoplastic resin composition can be improved by including the nucleating agent in the above content range.

The average particle diameter of the nucleating agent may be 100 占 퐉 or less. For example, the average particle diameter of the nucleating agent may be 1 to 100 mu m. For example, the average particle diameter of the nucleating agent may be 1 to 50 mu m or less. For example, the average particle diameter of the nucleating agent may be 1 to 30 mu m or less. The heat resistance of the thermoplastic resin composition can be further improved by using the nucleating agent having the above-mentioned particle size range.

As the nucleating agent, those which are generally used as a nucleating agent of the resin composition can be used, and either an inorganic nucleating agent or an organic nucleating agent can be used. Specific examples of the inorganic nucleating agent include talc, kaolinite, montmorillonite, synthetic mica, clay, zeolite, silica, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, emulsified calcium, boron nitride, calcium carbonate, And metal salts of neodymium and phenylphosphonate. For example, talc, mica, silica may be used. In particular, talc may be used.

Specific examples of the organic nucleating agent include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, calcium oxalate, sodium laurate, potassium laurate, sodium myristate, Sodium stearate, calcium stearate, magnesium stearate, magnesium stearate, barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, sodium carboxymethylcellulose, sodium carboxymethylcellulose, sodium carboxymethylcellulose, sodium carboxymethylcellulose, An organic carboxylic acid metal salt such as sodium salicylate, potassium salicylate, zinc salicylate, aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium beta -naphthalate and sodium cyclohexanecarboxylate, sodium p-toluenesulfonate, Organic sulfonic acid salts such as sodium phthalate, A carboxylic acid amide such as arginic acid amide, ethylene bislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide and trimethic acid tris (t-butyl amide), low density polyethylene, high density polyethylene, poly Propylene, polyisoprene, polybutene, poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, sodium salt of ethylene- acrylic acid or methacrylic acid copolymer, styrene Sodium salt or potassium salt (so-called ionomer), benzylidene sorbitol and its derivatives of a polymer having a carboxyl group such as sodium salt of maleic anhydride copolymer, phosphate ester such as NA-11 and NA-71 such as ADEKA Metal salts, and 2,2-methylbis (4,6-di-t-butylphenyl) sodium. For example, phosphoric acid ester metal salts such as ethylene bis lauric acid amide, benzylidene sorbitol and its derivatives, organic carboxylic acid metal salt, carboxylic acid amide, NA-11 and NA-71 manufactured by ADEKA can be used. The nucleating agent may be used singly or in combination of two or more.

The thermoplastic resin composition may be in the form of a liquid or a solid, and may be a composition before molding the final product, or a molded article, film, fabric or the like after being molded into a final product. The molded articles, fabrics, films, and the like may be manufactured by a conventional method depending on the shape of each product.

The thermoplastic resin composition may further include additives commonly used in conventional resin compositions described below.

For example, the additive may be selected from the group consisting of fillers, end blockers, metal deactivators, antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, tackifiers, plasticizers, viscosity modifiers, antistatic agents, , A polymerization inhibitor, and the like within a range that does not impair the physical properties of the resin composition.

Further, the thermoplastic resin composition may contain a filler. As the filler, an inorganic filler such as anhydrous amorphous aluminum silicate obtained by acid treatment and heat treatment of talc, wollastonite, mica, clay, montmorillonite, smectite, kaolin, zeolite (aluminum silicate) and zeolite can be used . When the filler is contained, the content of the filler in the resin composition may be 1 to 20% by weight based on the total weight of the resin composition to maintain the impact strength of the molded article.

The thermoplastic resin composition may contain a carbodiimide compound such as a polycarbodiimide compound or a monocarbodiimide compound as a terminal blocking agent. When the compound reacts with a part or all of the terminal carboxyl groups of the polylactic acid resin, side reactions such as hydrolysis are blocked, and the water resistance of the molded article containing the thermoplastic resin composition can be improved. Therefore, the durability of the molded article containing the thermoplastic resin composition under a high temperature and high humidity environment can be improved.

Examples of the polycarbodiimide compound include poly (4,4'-diphenylmethanecarbodiimide), poly (4,4'-dicyclohexylmethanecarbodiimide), poly (1,3,5-tri (Isopropylbenzene) polycarbodiimide, poly (1,3,5-triisopropylbenzene and 1,5-diisopropylbenzene) polycarbodiimide, and the like. The monocarbodiimide compound may be, for example, N, N'-di-2,6-diisopropylphenylcarbodiimide or the like.

The content of the carbodiimide compound may be 0.1 to 3% by weight based on the total weight of the thermoplastic resin composition. If the content is less than 0.1% by weight, improvement in durability of the molded article is insignificant, and if the content is more than 3% by weight, the mechanical strength of the molded article may be deteriorated.

The thermoplastic resin composition may contain a stabilizer or a colorant to stabilize the molecular weight or hue during molding. Examples of the stabilizer include phosphorus stabilizers, hindered phenol stabilizers, ultraviolet absorbers, heat stabilizers, antistatic agents and the like.

As the phosphorus stabilizer, phosphorous acid, phosphoric acid, phosphonic acid and esters thereof (phosphite compound, phosphate compound, phosphonite compound, phosphonate compound, etc.) and tertiary phosphine may be used.

Sandostab P-EPQ (Clariant), Irgafos P-EPQ (CIBA SPECIALTY CHEMICALS) and the like can be used as a stabilizer containing a phosphonite compound as a main component.

PEP-24 (Great Lakes), Ultranox P626 (GE Specialty Chemicals), PEP-8 (Asahi Kogyo Co.), JPP681S (Tohoku Kagaku Kogyo) , Doverphos S-9432 (Dover Chemical), Irgaofos 126, 126 FF (CIBA SPECIALTY CHEMICALS), PEP-36 (Asahi Telephone Industry), PEP-45 (Asahi Telephone Industry), Doverphos S-9228 have.

As the hindered phenolic stabilizer (antioxidant), a common compound compounded in a conventional resin can be used. The hindered phenolic stabilizer can be, for example, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1- , 4,8,10-tetraoxaspiro [5,5] undecane, and the like, but not limited thereto, and any hindered phenol compound used as an oxidation stabilizer of the resin composition in the art can be used.

The content of the phosphorus stabilizer and the hindered phenol antioxidant in the thermoplastic resin composition may be from 0.005 to 1% by weight based on the total weight of the resin composition.

The thermoplastic resin composition may comprise an ultraviolet absorber. By including the ultraviolet absorber, deterioration of the weather resistance of the molded article due to the influence of the rubber component or the flame retardant can be suppressed. A benzophenone-based ultraviolet absorber as an ultraviolet absorber; Ultraviolet absorbers based on benzotriazole; Ultraviolet absorbers based on hydroxyphenyltriazine; Cyclic imino ester-based ultraviolet absorbers; A cyanoacrylate-based ultraviolet absorber and the like can be used. The content of the ultraviolet absorber in the thermoplastic resin composition may be 0.01 to 2% by weight based on the total weight of the resin composition.

The thermoplastic resin composition may contain a dye or a pigment as a coloring agent in order to impart various colors to a molded article.

The thermoplastic resin composition may contain an antistatic agent to impart antistatic properties to the molded article.

The thermoplastic resin composition may contain a thermoplastic resin other than the above, a flow modifier, an antimicrobial agent, a dispersant such as liquid paraffin, a photocatalyst contaminant, a heat ray absorbent, and a photochromic lacquer.

The impact strength of the thermoplastic resin composition may be 110 J / m or more. For example, the impact strength of the thermoplastic resin composition may be 110 to 800 J / m. The impact strength of the thermoplastic resin composition may be 120 to 800 J / m. For example, the impact strength of the thermoplastic resin composition may be 250 to 800 J / m. For example, the impact strength of the thermoplastic resin composition may be 7500 to 800 J / m. When the thermoplastic resin composition has an impact strength of 110 J / m or more, the article produced using the thermoplastic resin composition can have improved durability.

The melting point (Tm_sc) of the stereocomplex formed by bonding of the first thermoplastic polymer and the second thermoplastic polymer contained in the thermoplastic resin composition may be 180 ° C or higher. For example, the melting point (Tm_sc) of the stereocomplex in the thermoplastic resin composition may be 180 ° C or higher. For example, the melting point (Tm_sc) of the stereocomplex in the thermoplastic resin composition may be 184 캜 or higher. For example, the melting point (Tm_sc) of the stereocomplex in the thermoplastic resin composition may be 190 캜 or higher. For example, the melting point (Tm_sc) of the stereocomplex in the thermoplastic resin composition may be 195 占 폚 or higher. By having the point that the stereocomplex contained in the thermoplastic resin composition melts at 180 占 폚 or more, it is possible to provide the article produced using the thermoplastic resin composition with improved heat resistance.

The molded article according to another embodiment consists of the thermoplastic resin fired body described above. The molded product can be obtained by melt-kneading each component constituting the resin composition by various extruders, Banbury mixers, kneaders, continuous kneaders, rolls or the like have. At the time of kneading, each of the above components may be added in bulk or added in portions and kneaded. The thermoplastic resin composition thus produced is subjected to injection molding, press molding, calendar molding, T die extrusion molding, hollow sheet extrusion molding, foam sheet extrusion molding, inflation molding, lamination molding, vacuum molding, A molded article can be obtained by a known molding method such as a combination molding method.

In the case where a kneading machine such as a calender molding machine, a T-die extrusion molding machine or an inflation molding machine is connected to a kneading extruder or a Banbury mixer, A molded article can be produced at the same time as it is obtained.

The molded article produced using the thermoplastic resin composition can be used in various applications without limitation. For example, the molded article can be used as an interior material and an exterior material of various general-purpose articles. For example, the molded article can be used as an interior material and an exterior material of household appliances, communication devices, industrial devices, and the like. The molded article may be a case such as a relay case, a wafer case, a reticle case, and a mask case; A carrier such as a liquid crystal tray, a chip tray, a hard disk tray, a CCD tray, an IC tray, an organic EL tray, an optical pickup tray, an LED tray, and an IC carrier; A protective film such as a polarizing film, a light guide plate, and various lenses; a sheet or film used in a clean room such as a sheet or a partition plate upon cutting a polarizing film; It can also be used in general purpose products such as electrification bags used in vending machines, liquid crystal panels, hard disks, plasma panels, conveying cases such as plastic corrugated boards, liquid crystal panels, liquid crystal cells, plasma panels, . In addition, the molded article can be used for medical applications such as vascular graft, cell carrier, drug carrier, and gene carrier.

The present invention will be described in more detail by way of the following examples and comparative examples. However, the examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

 (Preparation of block copolymer)

Example 1: Preparation of block copolymer [7 (random) (CL / LD = 86/14): 3 (block)]

12 g of? -Caprolactone (CLN) and 2 g of D-lactide (DLD) were introduced into a 250 ml glass reactor equipped with a stirrer, a heating device, a condenser and a vacuum apparatus under nitrogen atmosphere and stirred at 120 rpm After the temperature was raised to remove moisture, 0.5 wt% of Sn (Oct) ₂ (tin (II) 2-ethylhexanoate) as a catalyst was further added thereto and polymerization was carried out at 150 ° C for 1 hour. After the polymerization was completed, unreacted caprolactone and D-lactide were removed from the polymerization product under a vacuum of 20 torr using a vacuum pump to obtain a random copolymer of caprolactone and D-lactide.

6 g of D-lactide was added to the random copolymer, and 0.5 wt% of Sn (Oct) ₂ (tin (II) 2-ethylhexanoate) as a catalyst was further added thereto and polymerized at 150 ° C for 0.5 hour.

After the polymerization was completed, the polymerization product was dissolved in 120 g of chloroform, and then re-precipitated in 600 ml of methanol. The precipitate was dried in a 50 torr vacuum oven at 50 DEG C for 8 hours to remove unreacted D- A block copolymer to which a poly-D-lactic acid homopolymer block was added to the random copolymer block of caprolactone and D-lactide was obtained.

As a result of GPC (Gel Permeation Chromatography) analysis, the weight average molecular weight of the random copolymer was 42,000 and the weight average molecular weight of the block copolymer was 56,000.

GPC analysis was performed using polystyrene as a standard sample and tetrahydrofuran as a solvent.

DSC (Dynamic Scanning Calorimeter) analysis showed a first melting point due to the random copolymer block at 35 ° C and a second melting point due to the poly-D-lactic acid (PDLA) homopolymer block at 112 ° C. The DSC analysis was carried out at a rate of 10 ° C / min from 25 ° C to 170 ° C to analyze the melting point. The glass transition temperature (Tg) of the random copolymer was less than 0 占 폚.

Example 2: Preparation of block copolymer [7 (random) (CL / LD = 90/10): 3 (block)]

Polymerization was carried out in the same manner as in Example 1 except that the starting material for the random copolymer preparation was changed to 12.6 g of? -Caprolactone (CLN) and 1.4 g of D-lactide (DLD).

As a result of gel permeation chromatography (GPC) analysis, the weight average molecular weight of the random copolymer was 65,000 and the weight average molecular weight of the block copolymer was 77,000.

DSC (Dynamic Scanning Calorimeter) analysis showed a first melting point due to the random copolymer block at 46 ° C and a second melting point due to the poly-D-lactic acid (PDLA) homopolymer block at 146 ° C.

Example 3: Preparation of block copolymer [6 (random) (CL / LD = 90/10): 4 (block)]

The starting material for the random copolymer preparation was changed to 10.8 g of? -Caprolactone (CLN) and 1.2 g of D-lactide (DLD), and the amount of D-lactide added to the random copolymer was changed to 8 g The polymerization was carried out in the same manner as in Example 1,

As a result of GPC (gel permeation chromatography) analysis, the weight average molecular weight of the random copolymer was 46,000 and the weight average molecular weight of the block copolymer was 58,000.

DSC (Dynamic Scanning Calorimeter) analysis showed a first melting point due to the random copolymer block at 45 ° C and a second melting point due to the poly-D-lactic acid (PDLA) homopolymer block at 138 ° C.

Example 4: Preparation of block copolymer [5 (random) (CL / LD = 90/10): 5 (block)]

The starting material for the random copolymer preparation was changed to 9 g of? -Caprolactone (CLN) and 1 g of D-lactide (DLD), and the amount of D-lactide added to the random copolymer was changed to 10 g The polymerization was carried out in the same manner as in Example 1,

As a result of GPC (gel permeation chromatography) analysis, the weight average molecular weight of the random copolymer was 33,000 and the weight average molecular weight of the block copolymer was 54,000.

DSC (Dynamic Scanning Calorimeter) analysis showed a first melting point due to the random copolymer block at 44 ° C and a second melting point due to the poly-D-lactic acid (PDLA) homopolymer block at 150 ° C.

Comparative Example 1: Preparation of random copolymer [10 (random) (CL / LD = 90/10): 0 (block)]

18 g of? -Caprolactone (CLN) and 2 g of D-lactide (DLD) were introduced into a 250 ml glass reactor equipped with a stirrer, a heating device, a condenser and a vacuum device under nitrogen atmosphere and stirred at 120 rpm After the temperature was raised to remove moisture, 0.5 wt% of Sn (Oct) ₂ (tin (II) 2-ethylhexanoate) as a catalyst was further added thereto and polymerization was carried out at 150 ° C for 1.5 hours. After the polymerization was completed, the polymerization product was dissolved in 120 g of chloroform, and then reprecipitated in 600 ml of methanol. The precipitate was dried in a 50 torr vacuum oven for 8 hours to remove unreacted D-lactide , A random copolymer of the caprolactone and D-lactide was obtained.

GPC (Gel Permeation Chromatography) analysis showed that the weight average molecular weight of the random copolymer was 89,000.

DSC (Dynamic Scanning Calorimeter) analysis showed that melting point due to random copolymer appeared at 50 ℃.

Comparative Example 2: Preparation of block copolymer [7 (homo-block) (CL / LD = 100/0): 3 (block)]

14 g of ε-caprolactone (CLN) was added to a 250 ml glass reactor equipped with a stirrer, a heating device, a condenser and a vacuum device. The mixture was heated to 120 ° C. with stirring at 50 rpm to remove water. (Oct) ₂ (tin (II) 2-ethylhexanoate) of 0.5 wt% was added thereto, and polymerization was carried out at 150 ° C for 1 hour. After the polymerization was completed, unreacted caprolactone was removed from the polymerization product under a vacuum of 20 torr using a vacuum pump to obtain a caprolactone homopolymer.

6 g of D-lactide was added to the homopolymer, and 0.5 wt% of Sn (Oct) ₂ (tin (II) 2-ethylhexanoate) as a catalyst was further added thereto and polymerized at 150 ° C for 0.5 hour.

After the polymerization was completed, the polymerization product was dissolved in 120 g of chloroform, and then re-precipitated in 600 ml of methanol. The precipitate was dried in a 50 torr vacuum oven for 8 hours to remove unreacted D-lactide , A block copolymer to which the poly-D-lactic acid homopolymer block was added to the caprolactone homopolymer block was obtained.

As a result of gel permeation chromatography (GPC) analysis, the weight average molecular weight of the block copolymer was 92,000.

DSC (Dynamic Scanning Calorimeter) analysis showed a first melting point due to the caprolactone homopolymer block at 60 ° C and a second melting point due to the poly-D-lactic acid (PDLA) homopolymer block at 147 ° C.

Comparative Example 3: PLLA homopolymer

Polylactic acid homopolymer (PLLA) resin (NatureWorks (PLLA, poly-L-lactic acid, NatureWorks 4030D)) was used as it was.

DSC (Dynamic Scanning Calorimeter) analysis showed melting point of poly-L-lactic acid (PLLA) homopolymer at 168 ℃.

(Production of thermoplastic resin composition)

Example 5: [PLLA: block copolymer = 80: 20]

20 g of the block copolymer prepared in Example 1, 80 g of polylactic acid homopolymer (PLLA, poly-L-lactic acid, NatureWorks 4030D), 1 g of talc having an average particle diameter of 2 탆 and a modified plasticizer oil (ESO, 3 g of epoxidized soybean oil (Sigma-Aldrich) were dry blended and then extruded through a twin screw extruder (Thermo Scientific Process 11 micro twin) with a barrel diameter of 11 mm and a barrel length / barrel diameter (L / D) screw extruder) at a processing temperature of 200 ° C and a screw speed of 30 to 100 rpm to obtain a resin composition. The extrudate was dried at 40 ° C for 24 hours to prepare a resin composition.

As shown in FIG. 1, the thermoplastic resin composition has a structure in which a block copolymer is uniformly dispersed in a polylactic acid homopolymer (PLLA) matrix. Impact resistance is improved by absorbing external impact while the block copolymer is distributed in the matrix. The plasticizer is distributed and reacted at the interface between the block copolymer and the polymer homopolymer matrix to improve the binding force between the block copolymer and the matrix. Further, the block copolymer and the matrix form a stereocomplex, and heat resistance is improved.

Example 6: [PLLA: block copolymer = 85: 15]

A thermoplastic resin composition was prepared in the same manner as in Example 5 except that 15 g of the block copolymer prepared in Example 1 and 85 g of polylactic acid homopolymer (PLLA, poly-L-lactic acid, NatureWorks 4030D) Respectively.

Example 7: [PLLA: block copolymer = 90: 10]

A thermoplastic resin composition was prepared in the same manner as in Example 5 except that 10 g of the block copolymer prepared in Example 1 and 90 g of polylactic acid homopolymer (PLLA, poly-L-lactic acid, NatureWorks 4030D) Respectively.

Example 8: [PLLA: block copolymer = 80: 20]

A thermoplastic resin composition was prepared in the same manner as in Example 5, except that 20 g of the block copolymer prepared in Example 2 was used instead of 20 g of the block copolymer prepared in Example 1.

Example 9: [PLLA: block copolymer = 80: 20]

A thermoplastic resin composition was prepared in the same manner as in Example 5, except that 20 g of the block copolymer prepared in Example 3 was used instead of 20 g of the block copolymer prepared in Example 1.

Example 10: [PLLA: block copolymer = 80: 20]

A thermoplastic resin composition was prepared in the same manner as in Example 5, except that 20 g of the block copolymer prepared in Example 4 was used instead of 20 g of the block copolymer prepared in Example 1.

Comparative Example 4: [PLLA: random copolymer = 80: 20]

A thermoplastic resin composition was prepared in the same manner as in Example 10, except that 20 g of the random copolymer prepared in Comparative Example 1 was used instead of 20 g of the block copolymer prepared in Example 1.

Comparative Example 5: [PLLA: block copolymer = 80: 20]

A thermoplastic resin composition was prepared in the same manner as in Example 10, except that 20 g of the block copolymer prepared in Comparative Example 2 was used instead of 20 g of the block copolymer prepared in Example 1.

Comparative Example 6: [PLLA: block copolymer = 100: 0]

A thermoplastic resin composition was prepared in the same manner as in Example 10 except that only 100 g of the PLLA homopolymer of Comparative Example 3 and no plasticizer and talc were added.

Evaluation Example 1: Impact strength measurement

The thermoplastic resin composition extrudates prepared in Examples 5 to 10 and Comparative Examples 4 to 6 were dried in an oven at 50 ° C for 8 hours and then melt-kneaded at a resin melting temperature of 200 ° C using a thermo Scientific Haake Minijet Injection Molding System (64 mm (Length) ㅧ 12 mm (Width) ㅧ 32 (Depth)) according to ASTM D526 under the conditions of injection pressure of 750 bar, molding temperature of 100 캜 and injection time of 7 minutes. Izod impact strength was measured by a notched Izod impact test according to ASTM D256 method. The results are shown in Table 1 below.

Evaluation Example 2: Measurement of thermal stability

The glass transition temperature (T _g ), crystallization temperature (T _c ) and melting point (T _m ) of the thermoplastic resin compositions prepared in Examples 5 to 10 and Comparative Examples 4 to 6 were measured using a DSC (Dynamic Scanning Calorimeter) Respectively. The results are shown in Table 1 below.

For example, as shown in FIG. 2, DSC analysis of the thermoplastic resin composition of Example 5 revealed melting points corresponding to the polylactic acid homopolymer and polylactic acid forming the stereocomplex, respectively.

Izod impact strength
[J / m] T _g
[° C] T _c
[° C] T _{m_h}
[° C] T _{m_sc}
[° C] Example 5 812 42/65 96 170 185 Example 6 499 63 97 169 184 Example 7 114 60 99 170 184 Example 8 514 - 94 169 198 Example 9 200 62 93 169 196 Example 10 145 60 94 170 198 Comparative Example 4 87 - 108 170 - Comparative Example 5 100 42 94 169 199 Comparative Example 6 49 - - 168 -

Tg: glass transition temperature

Tc: crystallization temperature

Tm_h: melting point of homopolylactic acid

Tm_sc: Melting point of stereo complex polylactic acid

As shown in Table 1, the thermoplastic resin composition containing the block copolymer containing the random copolymer blocks of Examples 5 to 10 contained the thermoplastic resin composition containing only the random copolymer of Comparative Example 4, the thermoplastic resin composition of Comparative Example 5 The impact strength was remarkably improved as compared with the thermoplastic resin composition containing the block copolymer containing no random copolymer and the thermoplastic resin composition comprising the polylactic acid homopolymer of Comparative Example 6. In addition, the thermoplastic resin compositions of Examples 5 to 10 were also excellent in heat resistance.

Claims (20)

A first thermoplastic polymer; And
And a second thermoplastic polymer,
Wherein the first thermoplastic polymer is a block copolymer comprising a plurality of polymer blocks, at least one of the plurality of polymer blocks including a random copolymer,
Wherein the at least one structural unit of the first thermoplastic polymer and the structural unit of the second thermoplastic polymer are stereoisomers. The thermoplastic resin composition according to claim 1, wherein the random copolymer is selected from the group consisting of an ether monomer, an olefin monomer, a vinyl monomer, a polyol monomer, a polyvalent acid monomer, an isocyanate monomer, an acrylate monomer, a vinyl alcohol monomer, Wherein the thermoplastic resin composition comprises a structural unit derived from at least two monomers selected from the group consisting of monomers, silicon monomers, fluorine monomers and lactone monomers. The method according to claim 1, wherein the random copolymer is selected from the group consisting of lactic acid, styrene, vinylnaphthalene, methyl methacrylate, caprolactone, valerolactone, butyrolactone, butadiene, isobutylene, styrene-butadiene, methylsiloxane, , 1-butene, 4-methyl-pentene, norbornyl ethyl styrene, hexamethyl carbonate, hexyl norbornene, butyl succinate, dicyclopentadiene, cyclohexyl ethylene, 4-vinylpyrrolidone, 4-vinylpyridine, isoprene, 3-hydroxybutyrate, 2-hydroxymethacrylate, N-vinyl-2-pyrrolidone, 4-acryloylmorpholine, ethylene oxide, ethylene glycol, acrylonitrile, 2 selected from the group consisting of an oil derivative, propylene glycol, tetramethylene ether glycol, para-dioxanone, propylene carbonate, tetramethylene adipate, terephthalate, butylene adipate, and butylene succinate The thermoplastic resin composition containing a structural unit derived from monomer. The thermoplastic resin composition according to claim 1, wherein the random copolymer comprises a first structural unit derived from D-lactic acid and a second structural unit derived from a monomer having a structure different from D-lactic acid. 5. The thermoplastic resin composition according to claim 4, wherein the random copolymer comprises a second structural unit derived from caprolactone. The thermoplastic resin composition according to claim 4, wherein the random copolymer comprises 10 to 50% by weight of the first structural unit and 50 to 90% by weight of the second structural unit. The thermoplastic resin composition according to claim 1, wherein the random copolymer has a glass transition temperature (Tg) of less than 0 占 폚. The thermoplastic resin composition according to claim 1, wherein the random copolymer has a weight average molecular weight of 30,000 to 100,000. The thermoplastic resin composition according to claim 1, wherein the block copolymer comprises a first polymer block comprising a random copolymer and a second polymer block comprising a homopolymer. The thermoplastic resin composition according to claim 9, wherein the homopolymer is poly-D-lactic acid. The thermoplastic resin composition according to claim 9, wherein the block copolymer comprises 50 to 90% by weight of the first polymer block and 10 to 50% by weight of the second polymer block. The thermoplastic resin composition according to claim 1, wherein the block copolymer has a weight average molecular weight of 50,000 to 150,000. The thermoplastic resin composition according to claim 1, wherein the block copolymer comprises a first melting point of 30 to 60 占 폚 and a second melting point of 110 to 170 占 폚. The thermoplastic resin composition according to claim 1, wherein the second thermoplastic polymer is poly-L-lactic acid. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises 5 to 30% by weight of the first thermoplastic polymer relative to the total weight of the thermoplastic resin composition. The thermoplastic resin composition according to claim 1, which comprises 65 to 90% by weight of a second thermoplastic polymer relative to the total weight of the thermoplastic resin composition. The thermoplastic resin composition according to claim 1, further comprising a plasticizer. The thermoplastic resin composition according to claim 1, wherein the plasticizer comprises a vegetable plasticizer. The thermoplastic resin composition according to claim 1, which comprises 5 to 30% by weight of the first thermoplastic polymer, 65 to 90% by weight of the second thermoplastic polymer, and 1 to 5% by weight of the plasticizer based on the total weight of the thermoplastic resin composition. A molded article comprising the thermoplastic resin fired product according to any one of claims 1 to 19.

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